Method for making a hydroprocessing catalyst

ABSTRACT

The present invention is directed to a method for making a catalyst for hydroprocessing a carbonaceous feedstock under hydroprocessing conditions, and the use of that catalyst. More particularly, the present invention is directed to methods for inhibiting rapid decomposition of ammonium nitrate during calcination of the catalyst following metal impregnation, wherein ammonium nitrate is formed when a nitrate-containing composition and an ammonium-containing component is used in the deposition of metal onto the catalyst.

CROSS REFERENCE TO RELATED APPLICATIONS

The present invention is a divisional application of and claims priority to U.S. application Ser. No. 12/960,794, filed Dec. 6, 2010. Priority is also hereby claimed to U.S. provisional application No. 61/267,077 filed on Dec. 6, 2009. Both of the foregoing applications are hereby expressly incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

The present invention is directed to a method for making a catalyst for hydroprocessing a carbonaceous feedstock under hydroprocessing conditions. More particularly, the present invention is directed to methods for inhibiting a rapid acid-catalyzed decomposition of ammonium nitrate during calcination of the catalyst following metal impregnation, wherein the ammonium nitrate is formed when a nitrate-containing composition and an ammonium-containing component are used in the deposition of metal onto the catalyst.

BACKGROUND OF THE INVENTION

Catalytic hydroprocessing refers to petroleum refining processes in which a carbonaceous feedstock is brought into contact with hydrogen and a catalyst, at a higher temperature and pressure, for the purpose of removing undesirable impurities and/or converting the feedstock to an improved product. Examples of hydroprocessing processes include hydrotreating, hydrodemetalization, hydrocracking and hydroisomerization processes.

A hydroprocessing catalyst typically consists of one or more metals deposited on a support or carrier consisting of an amorphous oxide and/or a crystalline microporous material (e.g. a zeolite). The selection of the support and metals depends upon the particular hydroprocessing process for which the catalyst is employed.

In general, during catalyst manufacture, it has long been known that use of a nitrate-containing salt as a source for depositing one or more metals on a support, in conjunction with an ammonium-containing component, will result in the presence of ammonium nitrate and nitric acid on the final product and waste stream. (See, Pemicone, Catalysis Today, vol. 34, pp. 535-547, 1997). This is highly undesirable as removal of the ammonium nitrate from the waste stream is difficult and costly. In addition, during calcination of the catalyst, ammonium nitrate will undergo an acid catalyzed rapid exothermic decomposition, which could be potentially hazardous to manufacturing equipment and will typically destroy the catalyst extrudates. (See, Wood and Wise, The Journal of Chemical Physics, vol. 23, pp. 693-696, 1955).

Ammonium nitrate and/or the nitric acid can be removed from the catalyst product prior to calcination by washing the product with water. However, this method produces an additional waste stream, and may not predictably remove a sufficient amount of the nitric acid to ensure the absence of an acid-catalyzed thermal event during calcination of the product catalyst.

In addition, where a modifying agent such as citric acid is employed during the deposition of the metals onto the support, a washing step would be undesirable, as this would result in the removal of a large concentration of the deposited metals and modifying agent as well.

Accordingly, there is a current need for a method for inhibiting rapid decomposition of ammonium nitrate on catalyst products in the calcination process, when a nitrate-containing composition is used in the deposition of active metals on the catalyst.

SUMMARY OF THE INVENTION

The present invention is directed to a method for making a hydroprocessing catalyst containing at least one catalyst support, one or more metals, optionally one or more molecular sieves, and optionally one or more promoters.

In general, metal deposition is achieved by contacting the catalyst support with an impregnation solution. The impregnation solution contains at least one metal nitrate and has a pH between 1 and 5.5, inclusive (1≦pH≦5.5). In one subembodiment, the impregnation solution further contains a modifying agent described herein below.

In one embodiment, a shaped hydroprocessing catalyst is prepared by:

(a) forming an extrudable mass containing the catalyst support,

(b) extruding the mass to form a shaped extrudate,

(c) calcining the mass to form a calcined extrudate,

(d) contacting the shaped extrudate with an impregnation solution containing at least one metal nitrate and having a pH between 1 and 5.5, inclusive (1≦pH≦5.5), and

(e) drying the impregnated extrudate at a temperature sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.

In a subembodiment, a shaped hydroprocessing catalyst is prepared by:

(a) forming an extrudable mass containing the catalyst support,

(b) extruding the mass to form a shaped extrudate,

(c) calcining the mass to form a calcined extrudate,

(d) contacting the shaped extrudate with an impregnation solution containing at least one metal nitrate and a modifying agent, wherein the impregnation solution has a pH between 1 and 5.5, inclusive (1≦pH≦5.5), and

(e) drying the impregnated extrudate at a temperature below the decomposition temperature of the modifying agent and sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.

In another subembodiment, a shaped hydroprocessing catalyst is prepared by:

(a) forming an extrudable mass containing the catalyst support,

(b) extruding the mass to form a shaped extrudate,

(c) calcining the mass to form a calcined extrudate,

(d) contacting the shaped extrudate with an impregnation solution containing at least one metal nitrate and a modifying agent, wherein the impregnation solution has a pH between 1 and 5.5, inclusive (1≦pH≦5.5), and

(e) drying the impregnated extrudate at a temperature below the decomposition temperature of the modifying agent and sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.

(f) calcining the dried impregnated extrudate to remove the modifying agent and sufficient to convert at least one metal into oxide.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the results of a thermal gravimetric analysis of catalyst extrudates made with a pH correction (Catalyst D of Example 4) and without a pH correction (Catalyst B of Example 2).

FIG. 2 shows the results of a differential scanning calorimetry analysis of catalyst extrudates made with a pH correction (Catalyst D of Example 4) and without a pH correction (Catalyst B of Example 2).

DETAILED DESCRIPTION OF THE INVENTION Introduction

The term “Periodic Table” refers to the version of IUPAC Periodic Table of the Elements dated Jun. 22, 2007, and the numbering scheme for the Periodic Table Groups is as described in Chemical and Engineering News, 63(5), 27 (1985).

The term “bulk dry weight” to the weight of a material after calcination at elevated temperature of over 1000° C. for 30 minutes.

The term “hydroprocessing” refers to a process in which a carbonaceous feedstock is brought into contact with hydrogen and a catalyst, at a higher temperature and pressure, for the purpose of removing undesirable impurities and/or converting the feedstock to a desired product.

The term “hydrotreating” refers to a process that converts sulfur- and/or nitrogen-containing hydrocarbon feeds into hydrocarbon products with reduced sulfur and/or nitrogen content, typically in conjunction with a hydrocracking function, and which generates hydrogen sulfide and/or ammonia (respectively) as byproducts.

The term “hydrocracking” refers to a process in which hydrogenation and dehydrogenation accompanies the cracking/fragmentation of hydrocarbons, e.g., converting heavier hydrocarbons into lighter hydrocarbons, or converting aromatics and/or cycloparaffins (naphthenes) into non-cyclic branched paraffins

The term “hydroisomerization” refers to a process in which normal paraffins are isomerized to their more branched counterparts in the presence of hydrogen over a catalyst.

The term “hydrodemetalization” refers to a process that removes undesirable metals from hydrocarbon feeds into hydrocarbon products with reduced metal content.

The term “gas-to-liquid” (GTL) refers to a process in which gas-phase hydrocarbons such as natural gas are converted to longer-chain hydrocarbons such as diesel fuel via direct conversion or via syngas as an intermediate, for example using the Fischer-Tropsch process.

The term “framework topology” and its preceding three-letter framework code refers to the Framework Type data provided for the framework code in “Atlas of Zeolite Types” 6^(th) Edition, 2007.

The term “alkenyl,” as used herein, represents a straight or branched chain group of one to twelve carbon atoms derived from a straight or branched chain hydrocarbon containing at least one carbon-carbon double bond.

The term “hydroxyalkyl,” as used herein, represents one or more hydroxyl groups attached to the parent molecular moiety through an alkyl group.

The term “alkoxyalkyl,” as used herein, represents one or more alkoxy groups attached to the parent molecular moiety through an alkyl group.

The term “aminoalkyl,” as used herein, represents one or more amino groups attached to the parent molecular moiety through an alkyl group.

The term “oxoalkyl,” as used herein, represents one or more ether groups attached to the parent molecular moiety through an alkyl group.

The term “carboxyalkyl,” as used herein, represents one or more carboxyl groups attached to the parent molecular moiety through an alkyl group.

The term “aminocarboxyalkyl,” as used herein, represents one or more carboxyl groups and one or more amino groups attached to the parent molecular moiety through an alkyl group.

The term “hydroxycarboxyalkyl,” as used herein, represents one or more carboxyl groups and one or more hydroxyl groups attached to the parent molecular moiety through an alkyl group.

Where permitted, all publications, patents and patent applications cited in this application are herein incorporated by reference in their entirety; to the extent such disclosure is not inconsistent with the present invention.

Unless otherwise specified, the recitation of a genus of elements, materials or other components, from which an individual component or mixture of components can be selected, is intended to include all possible sub-generic combinations of the listed components and mixtures thereof. Also, “include” and its variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that may also be useful in the materials, compositions and methods of this invention.

Properties for the materials described herein are determined as follows:

(a) Constrained index (CI): indicates the total cracking conversion of a 50/50 mixture of n-hexane and 3-methyl-pentane by a sample catalyst at 900° F. (482° C.), 0.68 WHSV. Samples are prepared according to the method described in U.S. Pat. No. 7,063,828 to Zones and Burton, issued Jun. 20, 2006.

(b) Brønsted acidity: determined by isopropylamine-temperature-programmed desorption (IPam TPD). Samples are pre-treated at 400-500° C. for 1 hour in flowing dry H₂. The dehydrated samples are then cooled down to 120° C. in flowing dry He and held at 120° C. for 30 minutes in a flowing He saturated with isopropylamine for adsorption. The isopropylamine-saturated samples are then heated up to 500° C. at a rate of 10° C./min in flowing dry He. The Brönsted acidity is calculated based on the weight loss vs. temperature by TGA and effluent gas stream monitored by Mass Spectrometer.

(c) SiO₂/Al₂O₃ Ratio (SAR): determined by ICP elemental analysis. A SAR of infinity (∞) represents the case where there is no aluminum in the zeolite, i.e., the mole ratio of silica to alumina is infinity. In that case the molecular sieve is comprised of essentially all of silica.

(d) Surface area: determined by N₂ adsorption at its boiling temperature. BET surface area is calculated by the 5-point method at P/P₀=0.050, 0.088, 0.125, 0.163, and 0.200. Samples are first pre-treated at 400° C. for 6 hours in the presence of flowing, dry N₂ so as to eliminate any adsorbed volatiles like water or organics.

(e) Micropore volume: determined by N₂ adsorption at its boiling temperature. Micropore volume is calculated by the t-plot method at P/P₀=0.050, 0.088, 0.125, 0.163, and 0.200. Samples are first pre-treated at 400° C. for 6 hours in the presence of flowing, dry N₂ so as to eliminate any adsorbed volatiles like water or organics.

(f) Mesopore pore diameter: determined by N₂ adsorption at its boiling temperature. Mesopore pore diameter is calculated from N₂ isotherms by the BJH method described in E. P. Barrett, L. G. Joyner and P. P. Halenda, “The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms.” J. Am. Chem. Soc. 73, 373-380, 1951. Samples are first pre-treated at 400° C. for 6 hours in the presence of flowing, dry N₂ so as to eliminate any adsorbed volatiles like water or organics.

(g) Total pore volume: determined by N₂ adsorption at its boiling temperature at P/P₀=0.990. Samples are first pre-treated at 400° C. for 6 hours in the presence of flowing, dry N₂ so as to eliminate any adsorbed volatiles like water or organics.

(h) Unit cell size: determined by X-ray powder diffraction.

(i) Alpha value: determined by an Alpha test adapted from the published descriptions of the Mobil Alpha test (P. B. Weisz and J. N. Miale, J. Catal., 4, 527-529, 1965; J. N. Miale, N. Y. Chen, and P. B. Weisz, J. Catal., 6, 278-87, 1966). The “Alpha Value” is calculated as the cracking rate of the sample in question divided by the cracking rate of a standard silica alumina sample. The resulting “Alpha” is a measure of acid cracking activity which generally correlates with number of acid sites.

Hydroprocessing Catalyst Composition

The present invention is directed to a hydroprocessing catalyst containing at least one catalyst support, one or more metals, optionally one or more molecular sieves, and optionally one or more promoters, wherein deposition of at least one of the metals is achieved in the presence of a modifying agent.

For each embodiment described herein, the catalyst support is selected from the group consisting of alumina, silica, zirconia, titanium oxide, magnesium oxide, thorium oxide, beryllium oxide, alumina-silica, alumina-titanium oxide, alumina-magnesium oxide, silica-magnesium oxide, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, titanium oxide-zirconia, silica-alumina-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide or silica-alumina-magnesium oxide, preferably alumina, silica-alumina, and combinations thereof.

In one subembodiment, the catalyst support is an alumina selected from the group consisting of γ-alumina, η-alumina, θ-alumina, δ-alumina, χ-alumina, and mixtures thereof.

In another subembodiment, the catalyst support is an amorphous silica-alumina material in which the mean mesopore diameter is between 70 Å and 130 Å.

In another subembodiment, the catalyst support is an amorphous silica-alumina material containing SiO₂ in an amount of 10 to 70 wt. % of the bulk dry weight of the carrier as determined by ICP elemental analysis, a BET surface area of between 450 and 550 m²/g and a total pore volume of between 0.75 and 1.05 mL/g.

In another subembodiment, the catalyst support is an amorphous silica-alumina material containing SiO₂ in an amount of 10 to 70 wt. % of the bulk dry weight of the carrier as determined by ICP elemental analysis, a BET surface area of between 450 and 550 m²/g, a total pore volume of between 0.75 and 1.05 mL/g, and a mean mesopore diameter is between 70 Å and 130 Å.

In another subembodiment, the catalyst support is a highly homogeneous amorphous silica-alumina material having a surface to bulk silica to alumina ratio (S/B ratio) of 0.7 to 1.3, and a crystalline alumina phase present in an amount no more than about 10 wt. %.

${{S/B}\mspace{14mu}{Ratio}} = \frac{\left( {{{Si}/{Al}}\mspace{14mu}{atomic}\mspace{14mu}{ratio}\mspace{14mu}{of}\mspace{14mu}{the}\mspace{14mu}{surface}\mspace{14mu}{measured}\mspace{14mu}{by}\mspace{14mu}{XPS}} \right)}{\left( {{{Si}/{Al}}\mspace{14mu}{atomic}\mspace{14mu}{ratio}\mspace{14mu}{of}\mspace{14mu}{the}\mspace{14mu}{bulk}\mspace{14mu}{measured}\mspace{14mu}{by}\mspace{14mu}{elemental}\mspace{14mu}{analysis}} \right)}$

To determine the S/B ratio, the Si/Al atomic ratio of the silica-alumina surface is measured using x-ray photoelectron spectroscopy (XPS). XPS is also known as electron spectroscopy for chemical analysis (ESCA). Since the penetration depth of XPS is less than 50 Å, the Si/Al atomic ratio measured by XPS is for the surface chemical composition.

Use of XPS for silica-alumina characterization was published by W. Daneiell et al. in Applied Catalysis A, 196, 247-260, 2000. The XPS technique is, therefore, effective in measuring the chemical composition of the outer layer of catalytic particle surface. Other surface measurement techniques, such as Auger electron spectroscopy (AES) and Secondary-ion mass spectroscopy (SIMS), could also be used for measurement of the surface composition.

Separately, the bulk Si/Al ratio of the composition is determined from ICP elemental analysis. Then, by comparing the surface Si/Al ratio to the bulk Si/Al ratio, the S/B ratio and the homogeneity of silica-alumina are determined. How the SB ratio defines the homogeneity of a particle is explained as follows. An S/B ratio of 1.0 means the material is completely homogeneous throughout the particles. An S/B ratio of less than 1.0 means the particle surface is enriched with aluminum (or depleted with silicon), and aluminum is predominantly located on the external surface of the particles. The S/B ratio of more than 1.0 means the particle surface is enriched with silicon (or depleted with aluminum), and aluminum is predominantly located on the internal area of the particles.

For each embodiment described herein, the amount of catalyst support in the hydroprocessing catalyst is from 5 wt. % to 80 wt. % based on the bulk dry weight of the hydroprocessing catalyst.

For each embodiment described herein, the hydroprocessing catalyst may optionally contain one or more molecular sieves selected from the group consisting of BEA-, ISV-, BEC-, IWR-, MTW-, *STO-, OFF-, MAZ-, MOR-, MOZ-, AFI-, *NRE-, SSY-, FAU-, EMT-, ITQ-21-, ERT-, ITQ-33-, and ITQ-37-type molecular sieves, and mixtures thereof.

In one subembodiment, the one or more molecular sieves selected from the group consisting of molecular sieves having a FAU framework topology, molecular sieves having a BEA framework topology, and mixtures thereof.

The amount of molecular sieve material in the hydroprocessing catalyst is from 0 wt. % to 60 wt. % based on the bulk dry weight of the hydroprocessing catalyst. In one subembodiment, the amount of molecular sieve material in the hydroprocessing catalyst is from 0.5 wt. % to 40% wt. %.

In one subembodiment, the molecular sieve is a Y zeolite with a unit cell size of 24.15 Å-24.55 Å. In another subembodiment, the molecular sieve is a Y zeolite with a unit cell size of 24.15 Å-24.35 Å. In another subembodiment, the molecular sieve is a low-acidity, highly dealuminated ultrastable Y zeolite having an Alpha value of less than 5 and a Brønsted acidity of from 1 to 40. In one subembodiment, the molecular sieve is a Y zeolite having the properties described in Table 1 below.

TABLE 1 Alpha value 0.01-5   CI 0.05-10% Brønsted acidity 1-40 μmole/g SAR  80-150 surface area 650-750 m²/g micropore volume 0.25-0.30 mL/g total pore volume 0.51-0.55 mL/g unit cell size 24.15-24.35 Å

In another subembodiment, the molecular sieve is a Y zeolite having the properties described in Table 2 below.

TABLE 2 SAR 5-∞ micropore volume 0.15-0.27 mL/g BET surface area 700-825 m²/g unit cell size 24.15-24.55 Å

In another subembodiment, the catalyst contains from 0.1 wt. % to 40 wt. % (based on the bulk dry weight of the catalyst) of a Y zeolite having the properties described Table 2 above, and from 1 wt. % to 60 wt. % (based on the bulk dry weight of the catalyst) of a low-acidity, highly dealuminated ultrastable Y zeolite having an Alpha value of less than about 5 and Brønsted acidity of from 1 to 40 micro-mole/g.

As described herein above, the hydroprocessing catalyst of the present invention contains one or more metals. For each embodiment described herein, each metal employed is selected from the group consisting of elements from Group 6 and Groups 8 through 10 of the Periodic Table, and mixtures thereof. In one subembodiment, each metal is selected from the group consisting of nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W), and mixtures thereof. In another subembodiment, the hydroprocessing catalyst contains at least one Group 6 metal and at least one metal selected from Groups 8 through 10 of the periodic table. Exemplary metal combinations include Ni/Mo/W, Ni/Mo, Ni/W, Co/Mo, Co/W, Co/W/Mo and Ni/Co/W/Mo.

The total amount of metal oxide material in the hydroprocessing catalyst is from 0.1 wt. % to 90 wt. % based on the bulk dry weight of the hydroprocessing catalyst. In one subembodiment, the hydroprocessing catalyst contains from 2 wt. % to 10 wt. % of nickel oxide and from 8 wt. % to 40 wt. % of tungsten oxide based on the bulk dry weight of the hydroprocessing catalyst.

A diluent may be employed in the formation of the hydroprocessing catalyst. Suitable diluents include inorganic oxides such as aluminum oxide and silicon oxide, titanium oxide, clays, ceria, and zirconia, and mixture of thereof. The amount of diluent in the hydroprocessing catalyst is from 0 wt. % to 35 wt. % based on the bulk dry weight of the hydroprocessing catalyst. In one subembodiment, the amount of diluent in the hydroprocessing catalyst is from 0.1 wt. % to 25 wt. % based on the bulk dry weight of the hydroprocessing catalyst.

The hydroprocessing catalyst of the present invention may contain one or more promoters selected from the group consisting of phosphorous (P), boron (B), fluorine (F), silicon (Si), aluminum (Al), zinc (Zn), manganese (Mn), and mixtures thereof. The amount of promoter in the hydroprocessing catalyst is from 0 wt. % to 10 wt. % based on the bulk dry weight of the hydroprocessing catalyst. In one subembodiment, the amount of promoter in the hydroprocessing catalyst is from 0.1 wt. % to 5 wt. % based on the bulk dry weight of the hydroprocessing catalyst.

Preparation of the Hydroprocessing Catalyst

In the present invention, metal deposition is achieved by contacting at least the catalyst support with an impregnation solution. The impregnation solution contains at least one metal nitrate and has a pH between 1 and 5.5, inclusive (1≦pH≦5.5). In one subembodiment, the impregnation solution further contains a modifying agent described herein below.

In one embodiment, a shaped hydroprocessing catalyst is prepared by:

(a) forming an extrudable mass containing the catalyst support,

(b) extruding the mass to form a shaped extrudate,

(c) calcining the mass to form a calcined extrudate,

(d) contacting the shaped extrudate with an impregnation solution containing at least one metal nitrate and having a pH between 1 and 5.5, inclusive (1≦pH≦5.5), and

(e) drying the impregnated extrudate at a temperature sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.

In a subembodiment, a shaped hydroprocessing catalyst is prepared by:

(a) forming an extrudable mass containing the catalyst support,

(b) extruding the mass to form a shaped extrudate,

(c) calcining the mass to form a calcined extrudate,

(d) contacting the shaped extrudate with an impregnation solution containing at least one metal nitrate and a modifying agent, wherein the impregnation solution has a pH between 1 and 5.5, inclusive (1≦pH≦5.5), and

(e) drying the impregnated extrudate at a temperature below the decomposition temperature of the modifying agent and sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.

In another subembodiment, a shaped hydroprocessing catalyst is prepared by:

(a) forming an extrudable mass containing the catalyst support,

(b) extruding the mass to form a shaped extrudate,

(c) calcining the mass to form a calcined extrudate,

(d) contacting the shaped extrudate with an impregnation solution containing at least one metal nitrate and a modifying agent, wherein the impregnation solution has a pH between 1 and 5.5, inclusive (1≦pH≦5.5), and

(e) drying the impregnated extrudate at a temperature below the decomposition temperature of the modifying agent and sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.

(f) calcining the dried impregnated extrudate to remove the modifying agent and sufficient to convert at least one metal into oxide.

The diluent, promoter and/or molecular sieve (if employed) may be combined with the carrier when forming the extrudable mass. In another embodiment, the carrier and (optionally) the diluent, promoter and/or molecular sieve can be impregnated before or after being formed into the desired shapes.

For each embodiment described herein, the impregnation solution has a pH between 1 and 5.5, inclusive (1≦pH≦5.5). In one subembodiment, the impregnation solution has a pH between 1.5 and 3.5, inclusive (1.5≦pH≦3.5).

Depending on the metal nitrates and other components used to form the impregnation solution, before the addition of a basic component the pH of the impregnation solution will typically have a pH of less than 1, and more typically a pH of about 0.5. By adding a basic component to the impregnation solution to affect a pH adjustment to 1 and 5.5, inclusive (1≦pH≦5.5), the acid concentration is eliminated or reduced to a level which, during calcination, does not acid-catalyze decomposition of the ammonium nitrate at a rate rapid enough to have a deleterious effect on the hydroprocessing catalyst. In one embodiment, the acid concentration is eliminated or reduced to a level which, during calcination, does not acid-catalyze decomposition of the ammonium nitrate at a rate rapid enough to have a deleterious effect on more than 10 wt. % of the bulk dry weight of the hydroprocessing catalyst (e.g. does not produce fines or fractured extrudates which account for more than 10 wt. % of the bulk dry weight of the post-calcined hydroprocessing catalyst),

The basic component can be any base which can dissolve in the solvent selected for the impregnation solution and which is not substantially deleterious to the formation of the catalyst or to the hydroprocessing performance of the catalyst, meaning that the base has less than a measurable effect on, or confer less than a material disadvantage to, the performance of the hydroprocessing catalyst. A base which is not substantially deleterious to the formation of the catalyst will not reduce catalyst activity by more than 10° F. (5.5° C.) based on the performance of the hydroprocessing catalyst without pH correction.

Where the hydroprocessing catalyst is to be used in a hydrocracking process, one suitable base is ammonium hydroxide. Where the hydroprocessing catalyst is to be used for non-hydrocracking processes such a hydrotreating, hydrofinishing, and hydroisomerization, bases which contain one or more elements from Groups 1 and 2 of the Periodic Table may be used. Exemplary bases include potassium hydroxide, sodium hydroxide, calcium hydroxide, and magnesium hydroxide.

In one subembodiment, deposition of at least one of the metals is achieved in the presence of a modifying agent is selected from the group consisting of compounds represented by structures (1) through (4), including condensated forms thereof:

wherein:

(1) R₁, R₂ and R₃ are independently selected from the group consisting of hydrogen; hydroxyl; methyl; amine; and linear or branched, substituted or unsubstituted C₁-C₃ alkyl groups, C₁-C₃ alkenyl groups, C₁-C₃ hydroxyalkyl groups, C₁-C₃ alkoxyalkyl groups, C₁-C₃ aminoalkyl groups, C₁-C₃ oxoalkyl groups, C₁-C₃ carboxyalkyl groups, C₁-C₃ aminocarboxyalkyl groups and C₁-C₃ hydroxycarboxyalkyl groups;

(2) R₄ through R₁₀ are independently selected from the group consisting of hydrogen; hydroxyl; and linear or branched, substituted or unsubstituted C₂-C₃ carboxyalkyl groups; and

(3) R₁₁ is selected from the group consisting of linear or branched, saturated and unsaturated, substituted or unsubstituted C₁-C₃ alkyl groups, C₁-C₃ hydroxyalkyl groups, and C₁-C₃ oxoalkyl groups.

Representative examples of modifying agents useful in this embodiment include 2,3-dihydroxy-succinic acid, ethanedioic acid, 2-hydroxyacetic acid, 2-hydroxy-propanoic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid, methoxyacetic acid, cis-1,2-ethylene dicarboxylic acid, hydroethane-1,2-dicarboxylc acid, ethane-1,2-diol, propane-1,2,3-triol, propanedioic acid, and α-hydro-ω-hydroxypoly(oxyethylene).

In an alternate embodiment, deposition of at least one of the metals is achieved in the presence of a modifying agent selected from the group consisting of N,N′-bis(2-aminoethyl)-1,2-ethane-diamine, 2-amino-3-(1H-indol-3-yl)-propanoic acid, benzaldehyde, [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetra-acetic acid, 1,2-cyclohexanediamine, 2-hydroxybenzoic acid, thiocyanate, thiosulfate, thiourea, pyridine, and quinoline.

The modifying agent impedes metal aggregation, thereby enhancing the activity and selectivity of the catalyst.

For each embodiment described herein, when employed, the amount of modifying agent in the pre-calcined hydroprocessing catalyst is from 2 wt. % to 18 wt. % based on the bulk dry weight of the hydroprocessing catalyst.

The calcination of the extruded mass will vary depending on the particular support selected. Typically, the extruded mass can be calcined at a temperature between 752° F. (400° C.) and 1200° F. (650° C.) for a period of between 1 and 3 hours.

Non-limiting examples of suitable solvents include water and C₁ to C₃ alcohols. Other suitable solvents can include polar solvents such as alcohols, ethers, and amines. Water is a preferred solvent. It is also preferred that the metal compounds be water soluble and that a solution of each be formed, or a single solution containing both metals be formed. The modifying agent can be prepared in a suitable solvent, preferably water. The three solvent components can be mixed in any sequence. That is, all three can be blended together at the same time, or they can be sequentially mixed in any order. In an embodiment, it is preferred to first mix the one or more metal components in an aqueous media, than add the modifying agent.

The amount of metal precursors and modifying agent (when employed) in the impregnation solution should be selected to achieve preferred ratios of metal to modifying agent in the catalyst precursor after drying.

The calcined extrudate is exposed to the impregnation solution until incipient wetness is achieved, typically for a period of between 1 and 100 hours (more typically between 1 and 5 hours) at room temperature to 212° F. (100° C.) while tumbling the extrudates, following by aging for from 0.1 to 10 hours, typically from about 0.5 to about 5 hours.

The drying step is conducted at a temperature sufficient to remove the impregnation solution solvent, but below the decomposition temperature of the modifying agent. In another embodiment, the dried impregnated extrudate is then calcined at a temperature above the decomposition temperature of the modifying agent, typically from about 500° F. (260° C.) to 1100° F. (590° C.), for an effective amount of time, to convert the metals to metal oxides. The present invention contemplates that when the impregnated extrudate is to be calcined, it will undergo drying during the period where the temperature is being elevated or ramped to the intended calcination temperature. This effective amount of time will range from about 0.5 to about 24 hours, typically from about 1 to about 5 hours. The calcination can be carried out in the presence of a flowing oxygen-containing gas such as air, a flowing inert gas such as nitrogen, or a combination of oxygen-containing and inert gases.

The dried and calcined hydroprocessing catalysts of the present invention can be sulfided to form an active catalyst. Sulfiding of the catalyst precursor to form the catalyst can be performed prior to introduction of the catalyst into a reactor (thus ex-situ presulfiding), or can be carried out in the reactor (in-situ sulfiding).

Suitable sulfiding agents include elemental sulfur, ammonium sulfide, ammonium polysulfide (RNH₄)₂S_(x)), ammonium thiosulfate ((NH₄)₂S₂O₃), sodium thiosulfate (Na₂S₂O₃), thiourea CSN₂H₄, carbon disulfide, dimethyl disulfide (DMDS), dimethyl sulfide (DMS), dibutyl polysulfide (DBPS), mercaptanes, tertiarybutyl polysulfide (PSTB), tertiarynonyl polysulfide (PSTN), aqueous ammonium sulfide.

Generally, the sulfiding agent is present in an amount in excess of the stoichiometric amount required to form the sulfided catalyst. In another embodiment, the amount of sulfiding agent represents a sulphur to metal mole ratio of at least 3 to 1 to produce a sulfided catalyst.

The catalyst is converted into an active sulfided catalyst upon contact with the sulfiding agent at a temperature of 150° F. to 900° F. (66° C. to 482° C.), from 10 minutes to 15 days, and under a H₂-containing gas pressure of 101 kPa to 25,000 kPa. If the sulfidation temperature is below the boiling point of the sulfiding agent, the process is generally carried out at atmospheric pressure. Above the boiling temperature of the sulfiding agent/optional components, the reaction is generally carried out at an increased pressure. As used herein, completion of the sulfidation process means that at least 95% of stoichiometric sulfur quantity necessary to convert the metals into for example, Co₉S₈, MoS₂, WS₂, Ni₃S₂, etc., has been consumed.

In one embodiment, the sulfiding can be carried out to completion in the gaseous phase with hydrogen and a sulfur-containing compound which is decomposable into H₂S. Examples include mercaptanes, CS₂, thiophenes, DMS, DMDS and suitable S-containing refinery outlet gasses. The gaseous mixture of H₂ and sulfur containing compound can be the same or different in the steps. The sulfidation in the gaseous phase can be done in any suitable manner, including a fixed bed process and a moving bed process (in which the catalyst moves relative to the reactor, e.g., ebullated process and rotary furnace).

The contacting between the catalyst precursor with hydrogen and a sulfur-containing compound can be done in one step at a temperature of 68° F. to 700° F. (20° C. to 371° C.) at a pressure of 101 kPa to 25,000 kPa for a period of 1 to 100 hrs. Typically, sulfidation is carried out over a period of time with the temperature being increased or ramped in increments and held over a period of time until completion.

In another embodiment of sulfidation in the gaseous phase, the sulfidation is done in two or more steps, with the first step being at a lower temperature than the subsequent step(s).

In one embodiment, the sulfidation is carried out in the liquid phase. At first, the catalyst precursor is brought in contact with an organic liquid in an amount in the range of 20% to 500% of the catalyst total pore volume. The contacting with the organic liquid can be at a temperature ranging from ambient to 248° F. (120° C.). After the incorporation of an organic liquid, the catalyst precursor is brought into contact with hydrogen and a sulfur-containing compound.

In one embodiment, the organic liquid has a boiling range of 200° F. to 1200° F. (93° C. to 649° C.). Exemplary organic liquids include petroleum fractions such as heavy oils, lubricating oil fractions like mineral lube oil, atmospheric gas oils, vacuum gas oils, straight run gas oils, white spirit, middle distillates like diesel, jet fuel and heating oil, naphthas, and gasoline. In one embodiment, the organic liquid contains less than 10 wt. % sulfur, and preferably less than 5 wt. %.

Hydroprocessing Processes and Feeds

The catalyst composition according to the invention can be used in the dry or calcined form, in virtually all hydroprocessing processes to treat a plurality of feeds under wide-ranging reaction conditions, e.g., at temperatures in the range of 200° to 450° C., hydrogen pressures in the range of 5 to 300 bar, and space velocities (LHSV) in the range of 0.05 to 10 h⁻¹. The hydroprocessing catalyst composition of the invention is particularly suitable for hydrotreating hydrocarbon feedstocks such as middle distillates, kero, naphtha, vacuum gas oils, and heavy gas oils.

Using the catalyst of the present invention, heavy petroleum residual feedstocks, cyclic stocks and other hydrocrackate charge stocks can be hydrocracked using the process conditions and catalyst components disclosed in U.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753. Typically, hydrocracking can be carried out using the catalyst of the present invention by contacting the feedstock with hydrogen and the catalyst at a temperature in the range of 175-485° C., hydrogen pressures in the range of 5 to 300 bar, and LHSV in the range of 0.1-30 h⁻¹.

During hydrotreatment, oxygen, sulfur and nitrogen present in the hydrocarbonaceous feed is reduced to low levels. Aromatics and olefins, if present in the feed, may also have their double bonds saturated. In some cases, the hydrotreating catalyst and hydrotreating conditions are selected to minimize cracking reactions, which can reduce the yield of the most desulfided product (typically useful as a fuel).

Hydrotreating conditions typically include a reaction temperature between 204-482° C., for example 315-454° C.; a pressure between 3.5-34.6 Mpa, for example 7.0-20.8 MPa; a feed rate (LHSV) of 0.5 hr⁻¹ to 20 hr⁻¹ (v/v); and overall hydrogen consumption of 300 to 2000 scf per barrel of liquid hydrocarbon feed (53.4-356 m³ H₂/m³ feed).

Hydroisomerization conditions are dependent in large measure on the feed used and upon the desired product. The hydrogen to feed ratio is typically between 0.089 to 5.34 SCM/liter (standard cubic meters/liter), for example between 0.178 to 3.56 SCM/liter. Generally, hydrogen will be separated from the product and recycled to the reaction zone. Typical feedstocks include light gas oil, heavy gas oils and reduced crudes boiling above about 177° C.

Lube oil may be prepared using the catalyst. For example, a C₂₀₊ lube oil may be made by hydroisomerizing the paraffin fraction of the feed. Alternatively, the lubricating oil may be made by hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock to obtain an effluent comprising a hydrocracked oil, and catalytically dewaxing the effluent at a temperature of at least about 200° C. and at a pressure between 0.103 and 20.7 Mpa gauge, in the presence of added hydrogen gas.

Using the catalyst of the present invention, a FT wax feed generated from a GTL process can be hydrocracked to diesel and jet fuels using by contacting the catalyst of the present invention by the process with hydrogen and the catalyst at a temperature in the range of 175-485° C., hydrogen pressures in the range of 5 to 300 bar, and LHSV in the range of 0.1-30 h¹.

The following examples will serve to illustrate, but not limit this invention.

EXAMPLE 1 Catalyst A Comparative Hydrocracking Catalyst

A comparative hydrocracking catalyst was prepared per the following procedure: 67 parts by weight silica-alumina powder (obtained from Sasol), 27 parts by weight pseudo boehmite alumina powder (obtained from Sasol), and 6 parts by weight of zeolite Y (obtained from Zeolyst) were mixed well. A diluted HNO₃ acid aqueous solution (1 wt. %) was added to the mix powder to form an extrudable paste. The paste was extruded in 1/12″ asymmetric quadrilobe shape, and dried at 250° F. (121° C.) overnight. The dried extrudates were calcined at 1100° F. (593° C.) for 1 hour with purging excess dry air, and cooled down to room temperature.

Impregnation of Ni and W was done using a solution containing ammonium metatungstate and nickel nitrate in concentrations equal to the target metal loadings of 3.7 wt. % NiO and 28 wt. % WO₃ based on the bulk dry weight of the finished catalyst. The total volume of the solution matched the 103% water pore volume of the base extrudate sample (incipient wetness method). The pH value of this solution was about 2.5. The metal solution was added to the base extrudates gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 250° F. (121° C.) overnight. The dried extrudates were calcined at 842° F. (450° C.) for 1 hour at a ramping rate of 10° C./min with purging excess dry air, and cooled down to room temperature. The catalyst extrudate remained intact during the calcination process. This catalyst is named Catalyst A and its physical properties are summarized in Table 3.

EXAMPLE 2 Catalyst B with Modifying Agent

Catalyst B was prepared using extrudates prepared with the same formulation as that for Catalyst A with the addition of 2-hydroxy 1,2,3-propanetricarboxylic acid as a modifying agent. Impregnation of Ni and W was done using a solution containing ammonium metatungstate and nickel nitrate in concentrations equal to the target metal loadings of 3.7 wt. % NiO and 28 wt. % WO₃ based on the bulk dry weight of the finished catalyst. 2-Hydroxy 1,2,3-propanetricarboxylic acid in an amount equal to 10 wt. % of the bulk dry weight of the finished catalyst, was added to the Ni/W solution. The solution was heated to above 120° F. (49° C.) to ensure a completed dissolved (clear) solution. The total volume of the metal solution matched the 103% water pore volume of the base extrudates (incipient wetness method). The pH value of the solution was about 0.5. The metal solution was added to the base extrudates gradually while tumbling the extrudates. When the solution addition was completed, the soaked extrudates were aged for 2 hours. Then the extrudates were dried at 400° F. (205° C.) for 2 hour with purging excess dry air.

EXAMPLE 3 Catalyst C Calcination of Catalyst B

Catalyst C was prepared by further calcination of Catalyst B to 842° F. (450° C.) for 1 hour at ramping rate of 10° C./min. It was found that the majority of extrudate catalyst shattered to smaller particles and fines. TGA analysis indicated that there was a rapid decomposition reaction occurred at ˜277° C. (FIG. 1) with a rapid heat release simultaneously as shown by DSC analysis (FIG. 2).

EXAMPLE 4 Catalyst D pH Adjustment to 2.5

Catalyst D was prepared with the same formulation as Catalyst B excepted for titration of Ni/W solution to pH=2.5 using ammonium hydroxide. The catalyst was dried at 400° F. (205° C.) for 2 hour with purging excess dry air, and cooled down to room temperature. TGA analysis indicated that the rapid decomposition peak on Catalyst B was not longer occurred on Catalyst D in the calcination process (FIG. 1). The rapid heat release is inhibited as well on Catalyst D as indicated by DSC experiment (FIG. 2).

EXAMPLE 5 Catalyst E Calcination of Catalyst D

Catalyst E was prepared by further calcination of Catalyst D at 842° F. (450° C.) for 1 hour at ramping rate of 10° C./min. The extrudates remained intact during the calcination process, consistent with TGA and DSC results in FIGS. 1 and 2.

EXAMPLE 6 Catalyst F With pH Correction to 1.0

Catalyst F was prepared with the same formulation as Catalyst B excepted for titration of Ni/W solution to pH=1.0 by ammonia solution. The impregnated extrudates was calcined at 400° F. (205° C.) for 2 hour and then at 842° F. (450° C.) for 1 hour with purging excess dry air. The extrudates were then cooled down to room temperature for inspections. There were some fines at the bottom of calcination container though there was no visible damage to the extrudates.

Table 3 compares the physical properties of catalysts made at different pH values. It shows little effect of pH value of metal solutions on the texture properties of finished catalysts.

TABLE 3 CATALYST A C E F Base Zeolite, wt. % 6 Silica Alumina, wt. % 67 Alumina, wt. % 27 Porosity by N₂ uptake Surface area, m²/g 439 Mean mesopore diameter, Å 77 Total pore volume, cc/g 0.65 CI test n-C₆ conversion, wt. % 1.8 i-C₆ conversion % 7.8 Finished Catalysts Metal content, wt. % NiO, wt. % 3.7 3.7 3.7 3.7 WO₃, wt. % 28 28 28 28 Porosity by N₂ uptake Surface area, m²/g 268 274 248 291 Mean mesopore diameter, Å 85 74 81 80 Total pore volume, cc/g 0.42 0.40 0.38 0.42

EXAMPLE 8 Hydrocracking Performance

A hydrotreated VGO feed was used to evaluate the hydrocracking performances of the catalysts. In each test, the catalyst was subjected to the following process conditions: 2000 PSIG total pressure (1900 PSIA H₂ at the reactor inlet), 5000 SCFB H₂, 1.0 LHSV, 70 wt. % conversion (<700° F./371° C.). Table 4 shows the feed properties.

TABLE 4 API Gravity 32.3 Sulfur, ppm wt. 16.1 Nitrogen, ppm wt. 0.5 Oxygen, wt. % 0 PCI 146 Components Paraffins, LV % 24.5 Naphthenes, LV % 57.4 Aromatics, LV % 17.7 ASTM D2887 SimDis, ° F. (° C.) 0.5 wt. %/5 wt. % 628/683 (331/362) 10 wt. %/30 wt. % 715/785 (379/418) 50 wt. % 837 (447) 70 wt. %/90 wt. % 883/956 (473/513) 95 wt. %/99.5 wt. % 1025/1235 (552/668) 

Table 5 compares the hydrocracking performance over catalysts prepared with and without a modifying agent and with and without pH correction. Catalyst C shows higher middle distillate yield (250-700° F. or 121-371° F.) than Catalyst A, indicating benefit of the use of modifying agent of 2-hydroxy 1,2,3-propanetricarboxylic acid. The modifying agent does not affect hydrocracking catalysis activity on the hydrotreated VGO feed. Table 5 indicates that Catalysts C, E and F have very comparable hydrocracking activity and distillate selectivity with hydrotreated Feed, suggesting very minor effect of pH adjustment on hydrocracking performance.

TABLE 5 Hydrocracking Performance with Feed 1 Catalyst Catalyst Catalyst Catalyst A C E F Modifying Agent No Yes Yes Yes pH value of metal solution 2.5 0.5 2.5 1.0 Extrudates after calcination at Intact Shat- Intact Intact but 842° F. (450° C.) tered with fine Catalyst Activity, ° F. (° C.) Base Base Base Base +1° F. +3° F. +2° F. (+0.6° (+1.7° (+1.1° C.) C.) C.) No Loss Yields, wt. % C₄- 3.4 3.2 3.2 3.1 C₅ - 250° F. (121° C.) 14.9 14.0 14.3 14.3 C₅ - 250-550° F. (121-288° C.) 41.2 41.3 40.9 41.3 C₅ - 550-700° F. (288-371° C.) 14.7 15.7 15.8 15.5 

What is claimed is:
 1. A method for hydroprocessing a carbonaceous feedstock, comprising contacting the carbonaceous feedstock with a sulfided hydroprocessing catalyst and hydrogen under hydroprocesssing conditions, the hydroprocessing catalyst comprising at least one metal deposited on a catalyst support, wherein the hydroprocessing catalyst is made by a method comprising the steps of: (a) forming an extrudable mass containing the catalyst support, (b) extruding the mass to form a shaped extrudate, (c) calcining the mass to form a calcined extrudate, (d) preparing an impregnation solution containing at least one metal nitrate, a modifying agent and an ammonium containing component, and adjusting the pH of the impregnation solution with a hydroxide to between 1 and 5.5, inclusive, (e) contacting the shaped extrudate with the impregnation solution, and (f) drying the impregnated extrudate at a temperature sufficient to remove the impregnation solution solvent, to form a dried impregnated extrudate.
 2. The method of claim 1, wherein the sulfided hydroprocessing catalyst further comprises at least one molecular sieve.
 3. The method of claim 2, wherein the molecular sieve is a Y zeolite with a unit cell size of between 24.15 Å and 24.55 Å.
 4. The method of claim 2, wherein the at least one molecular sieve is a Y zeolite having a silica-to-alumina ratio of greater than 5, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m²/g to 825 m²/g, and a unit cell size of from 24.15 Å to 24.55 Å.
 5. The method of claim 1, wherein the sulfided hydroprocessing catalyst further comprises a Y zeolite having a silica-to-alumina ratio of greater than 10, a micropore volume of from 0.15 mL/g to 0.27 mL/g, a BET surface area of from 700 m²/g to 825 m²/g, and a unit cell size of from 24.15 Å to 24.35 Å, and a low-acidity, highly dealuminated ultrastable Y zeolite having an Alpha value of less than about 5 and Brønsted acidity of from 1 to 40 micro-mole/g.
 6. The method of claim 1, wherein the modifying agent is selected from the groups consisting of compounds represented by structures (1) through (4), and condensated forms thereof:

wherein: (1) R₁, R₂ and R₃ are independently selected from the group consisting of hydrogen; hydroxyl; methyl; amine; and linear or branched, substituted or unsubstituted C₁-C₃ alkyl groups, C₁-C₃ alkenyl groups, C₁-C₃ hydroxyalkyl groups, C₁-C₃ alkoxyalkyl groups, C₁-C₃ aminoalkyl groups, C₁-C₃ oxoalkyl groups, C₁-C₃ carboxyalkyl groups, C₁-C₃ aminocarboxyalkyl groups and C₁-C₃ hydroxycarboxyalkyl groups; (2) R₄ through R₁₀ are independently selected from the group consisting of hydrogen; hydroxyl; and linear or branched, substituted or unsubstituted C₂-C₃ carboxyalkyl groups; and (3) R₁₁ is selected from the group consisting of linear or branched, saturated and unsaturated, substituted or unsubstituted C₁-C₃ alkyl groups, C₁-C₃ hydroxyalkyl groups, and C₁-C₃ oxoalkyl groups.
 7. The method of claim 1, wherein the modifying agent is selected from the group consisting of N,N′-bis(2-aminoethyl)-1,2-ethane-diamine, 2-amino-3-(1H-indol-3-yl)-propanoic acid, benzaldehyde, [[(carboxymethyl)imino]bis(ethylenenitrilo)]-tetra-acetic acid, 1,2-cyclohexanediamine, 2-hydroxybenzoic acid, thiocyanate, thiosulfate, thiourea, pyridine, and quinoline.
 8. The method of claim 1, wherein the at least one metal nitrate comprises a metal selected from the group consisting of elements from Group 6 and Groups 8 through 10 of the Periodic Table.
 9. The method of claim 8, wherein the at least one metal is selected from the group consisting of nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W), and mixtures thereof.
 10. The method of claim 1, wherein the hydroprocessing conditions comprise a temperature in the range of 175-485° C., hydrogen pressures in the range of 5 to 300 bar, and LHSV in the range of 0.1-30 h⁻¹.
 11. The method of claim 1, wherein the hydroprocessing conditions comprise a reaction temperature between 204-482° C., a feed rate (LHSV) of 0.5 hr⁻¹ to 20 hr⁻¹ (v/v), and an overall hydrogen consumption of 53.4 to 356 m³ H₂ per m³ of liquid hydrocarbon feed.
 12. The method of claim 1, wherein the hydroxide comprises ammonium hydroxide. 